Dental cement composition and method of use

Abstract

Provided herein are dental compositions and methods for use in dental cementing applications.

Description

[Technical Field]

[0001] Its applications include dental compositions, particularly those useful for dental cementation. [Background technology]

[0002] Dental restorations or fillings are dental restorative materials used to restore the function, unity, and form of lost tooth structure. Structural loss is usually due to caries or trauma (collectively referred to herein as cavities). Similarly, it can be intentionally lost during tooth preparation to improve aesthetics or the physical unity of the desired restorative material.

[0003] Dental cements are used in a variety of dental and orthodontic applications, including as luting agents, pulp-protecting agents, or cavity liner materials. Furthermore, they are used to form a protective layer under metal, resin, or ceramic restorations to protect the pulp from damage. They are useful for bonding, fixing, and casting inlays, onlays, or similar materials to both dentin and enamel.

[0004] Generally, resin cements are classified into two types: total etching and self-adhesive resin cements. For proper use, pure resin cements require pretreatment of the tooth surface, preferably with phosphoric acid, and application of dentin and enamel primers before the resin cement is applied. After curing, it forms a micromechanical bond in both dentin and enamel. They are also insoluble in oral fluids. These "conventional resin cements" (those requiring the use of "total etching and dentin bonding techniques") come in two types: dual-cure and light-curing. A recent addition to "resin cements" is self-adhesive resin cement, which does not require pretreatment of the tooth surface and appears to be easier to use than more traditional types of cement, while retaining many of the clinical advantages of conventional resin cement systems. It is important to note that, generally, the adhesive strength of self-etching resin cements is not as high as that of resin cements using total etching techniques, and as a result, microleakage at the edges is more likely to occur.

[0005] An ideal dental cement should offer strong and durable cementation along with ease of use. [Overview of the Initiative]

[0006] In certain embodiments, dental compositions comprising polymerizable monomers, as well as hydroperoxides and / or thioureas, are provided herein. In some embodiments, the compositions further comprise copper(II) (for example, as a catalyst).

[0007] This specification also provides dental compositions comprising an adhesive and a paste mixture on the surface of a dental substrate, wherein the adhesive comprises at least one phosphoric acid-containing (meth)acrylic monomer, and the paste mixture comprises at least one polymerizable monomer, at least one hydroperoxide, and at least one thiourea compound. Phosphate-containing (meth)acrylic monomers are selected from the group consisting of GPDM (glycerol phosphate di(meth)acrylate {(meth)acrylate = acrylate or methacrylate}), phenyl-P (phenyl methacrylate oxyethyl phosphate), PENTA-P (dipentaerythritol pentaacrylate phosphate), 10-MDP (methacryloyl oxydecyl phosphate), HEMA-P (hydroxyethyl methacrylate phosphate), HEA-P (hydroxyethyl acrylate phosphate), bis(HEMA)-P (bis(hydroxyethyl methacrylate) phosphate), bis(HEA)-P {bis(hydroxyethyl acrylate) phosphate), bis((meth)acryloyloxypropyl) phosphate, and combinations thereof. In certain embodiments, the phosphate-containing (meth)acrylic monomer is 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP). The thiourea is selected from the group consisting of 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2-tetrahydrofurfuryl)-2-thiourea (TTU), or combinations thereof. In certain embodiments, the thiourea is 1-(2-pyridyl)-2-thiourea (PTU). In certain embodiments, the hydroperoxide is a tertiary hydroperoxide. In certain embodiments, a first part or a second part of the paste mixture further comprises a copper(II) compound. In certain embodiments, the dental substrate is zirconia. In another embodiment, the adhesive is a single-bottle bonding agent.

[0008] Furthermore, this specification provides a dental restorative method comprising: a first step of applying a dental adhesive onto a dental substrate, wherein the adhesive contains at least one phosphoric acid-containing (meth)acrylic monomer; and a second step of applying a paste mixture from a device having a first part and a second part separated from each other, wherein the first part and the second part form a paste mixture, and the paste mixture from the device contains at least one polymerizable monomer and at least one hydroperoxide in the first part and at least one thiourea compound in the second part. In certain embodiments, the phosphoric acid-containing (meth)acrylic monomer is selected from the group consisting of GPDM (glycerol phosphate di(meth)acrylate {(meth)acrylate = acrylate or methacrylate}), phenyl-P (phenyl methacrylate oxyethyl phosphate), PENTA-P (dipentaerythritol pentaacrylate phosphate), 10-MDP (methacryloyl oxydecyl phosphate), HEMA-P (hydroxyethyl methacrylate phosphate), HEA-P (hydroxyethyl acrylate phosphate), bis(HEMA)-P (bis(hydroxyethyl methacrylate) phosphate), bis(HEA)-P {bis(hydroxyethyl acrylate) phosphate), bis((meth)acryloyloxypropyl) phosphate, and combinations thereof. In certain embodiments, the phosphoric acid-containing (meth)acrylic monomer is 10-methacryloyl oxydecyl dihydrogen phosphate (10-MDP). The thiourea is selected from the group consisting of 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2-tetrahydrofurfuryl)-2-thiourea (TTU), or a combination thereof. In certain embodiments, the thiourea is 1-(2-pyridyl)-2-thiourea (PTU). In certain embodiments, the hydroperoxide is a tertiary hydroperoxide. In certain embodiments, the first or second part of the paste mixture further comprises a copper(II) compound.The adhesive effectively adheres to the dental substrate. In certain embodiments, the dental substrate is zirconia. In certain embodiments, the adhesion strength of the dental adhesive on the dental substrate is greater than 15 MPa. In one embodiment, the device is a dual-barrel syringe.

[0009] Further provided is a dental composition, which includes an adhesive and a paste mixture on the surface of a dental substrate. The adhesive includes at least one phosphoric acid-containing (meth)acrylic monomer. The paste mixture is formed by mixing a pre-separated first portion and a second portion together. The first portion includes at least one polymerizable monomer and at least one hydroperoxide; the second portion includes at least one thiourea compound. In certain embodiments, the pre-separated first portion and second portion are separated by a dual-barrel syringe.

[0010] In other embodiments, the dental composition includes a first portion and a second portion. The first portion includes: a copper (II) catalyst; a hydroperoxide; and a polymerizable monomer containing an ethylenic group; and the second portion includes: a copper (II) catalyst; thiourea; and a polymerizable monomer containing an ethylenic group. In certain embodiments, the first portion and the second portion are physically separated (e.g., until such time as the dental composition is used to repair a dental cavity).

[0011] In some embodiments, provided herein is a dental composition including a first portion and a second portion, and the first portion and the second portion comprehensively include: a copper (II) catalyst; a hydroperoxide; a polymerizable monomer containing an ethylenic group; and thiourea. In certain embodiments, the first portion includes hydrogen peroxide, the second portion includes thiourea, and the first portion and the second portion are physically separated from each other (e.g., until such time as the dental composition is used to repair a dental cavity).

[0012] In some embodiments, provided herein are dental compositions, parts thereof, or resin precursors thereof, the composition comprising: a copper(II) catalyst; a hydroperoxide; and a polymerizable monomer (e.g., a polymerizable monomer containing an ethylenic group). Similarly, in certain embodiments, provided herein are dental compositions, parts thereof, or resin precursors thereof, the composition comprising: a copper(II) catalyst; thiourea; and a polymerizable monomer (e.g., a polymerizable monomer containing an ethylenic group).

[0013] In some embodiments, provided herein are dental compositions comprising a first and a second part (e.g., a fast-curing, copper-free, acid-free composition), wherein the first and second parts together comprise: a hydroperoxide (e.g., a hydroperoxide that is a tertiary aryl hydroperoxide such as cumene hydroperoxide (e.g., HOOCR'3 [wherein each R' is independently alkyl or aryl, and at least one R' is aryl (e.g., substituted or unsubstituted aryl)]); a polymerizable monomer (e.g., a polymerizable monomer containing an ethylenic group); and thiourea. In some embodiments, the first part comprises hydrogen peroxide, the second part comprises thiourea, and the first and second parts are physically separated from each other. In certain embodiments, the hydroperoxide is present in a concentration of about 1.5% (w / w) or more in the dental composition, or in a concentration of about 1.5% (w / w) or more relative to the monomer. In more specific embodiments, the hydroperoxide is present in a concentration of about 2% (w / w) or more in the dental composition, or in a concentration of about 2% (w / w) or more relative to the monomer. The concentration is approximately 2% (w / w) or higher. In a further specific embodiment, the hydroperoxide is present in a concentration of approximately 2.5% (w / w) or higher in the dental composition, or in a concentration of approximately 2.5% (w / w) or higher relative to the monomer. In a further or alternative embodiment, the thiourea is present in a concentration of approximately 1.5% (w / w) or higher in the dental composition, or in a concentration of approximately 1.5% (w / w) or higher relative to the monomer. In a more specific embodiment, the thiourea is present in a concentration of approximately 2% (w / w) or higher in the dental composition, or in a concentration of approximately 2% (w / w) or higher relative to the monomer. In a particular embodiment, the concentration of thiourea in the dental composition is approximately 2.5% (w / w) or more, or the concentration relative to the monomer is approximately 2.5% (w / w) or more. In a further or additional embodiment, the total weight of hydroperoxide and thiourea is approximately 3% (w / w) or more in the dental composition, or the concentration relative to the monomer is approximately 3% (w / w) or more. In a more specific embodiment, the total weight of hydroperoxide and thiourea is approximately 4% (w / w) or more in the dental composition, or the concentration relative to the monomer is approximately 4% (w / w) or more.In one more specific embodiment, the total weight of the hydroperoxide and thiourea is such that the concentration in the dental composition is about 5% (w / w) or more, or the concentration relative to the monomer is about 5% (w / w) or more.

[0014] In certain embodiments, the copper(II) catalyst comprises copper(II) ions and / or copper(II) compounds. In certain embodiments, the copper(II) catalyst comprises copper(II) sulfate, copper(II) acetate, copper(II) chloride, copper(II) acetylacetone, or a combination thereof. In some embodiments, the copper(II) catalyst is present in the composition in an amount of about 5% by weight or less (e.g., about 1% by weight or less, or about 0.1% by weight or less).

[0015] In some embodiments, the hydroperoxide is a hydrocarbon substituted with one or more -OOH groups (e.g., C4-C4). 20 The composition contains hydrocarbons. In certain embodiments, the hydroperoxide is a tertiary hydroperoxide (e.g., the -OOH group is substituted with a carbon having a tertiary substitution). In more specific embodiments, the hydroperoxide is t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinan hydroperoxide, p-menthane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, or a combination thereof, or comprising them. In further or alternative embodiments, the hydroperoxide is present in the composition in an amount of about 0.01% (w / w) to about 10% (w / w). In more specific embodiments, the hydroperoxide is present in the composition in an amount of about 0.1% (w / w) to about 5% (w / w). In some embodiments, the hydroperoxide is present in the composition in a ratio of about 1:9999 to about 1:9 of the hydroperoxide to the polymerizable monomer. In a more specific embodiment, the ratio of hydroperoxide to polymerizable monomer is approximately 1:99 to approximately 5:95.

[0016] In certain embodiments, the monomer is a dentally acceptable monomer. In some embodiments, the monomer includes vinyl, acrylate, methacrylate, or a combination thereof. In further or alternative embodiments, the monomer is present in amounts of about 10% (w / w) to about 60% (w / w). In more specific embodiments, the polymerizable monomer is present in amounts of about 20% (w / w) to about 50% (w / w).

[0017] In certain embodiments, thiourea includes 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2-tetrahydrofurfuryl)-2-thiourea (TTU), or combinations thereof. In further or alternative embodiments, thiourea is present in the composition in a ratio of about 1:999 to about 100:900 as thiourea to polymerizable monomers. In more specific embodiments, the ratio of thiourea to polymerizable monomers is about 1:99 to about 10:90.

[0018] In certain embodiments, the dental compositions provided herein include a filler. In more specific embodiments, a first part and a second part include a filler. In even more specific embodiments, the filler is a micronized filler. In some embodiments, the micronized filler includes a plurality of particles. In certain embodiments, the particles have an average size (e.g., diameter) of about 0.02 microns to about 30 microns, for example, about 0.2 microns to about 10 microns. In further or alternative embodiments, the filler includes an inorganic filler, a prepolymerized filler, or a combination thereof. Fillers include, in non-limiting examples, metal oxides, metal nitrides, metal fluorides, silicates, silica (e.g., colloidal silica, precipitated silica, fused silica), aluminosilicates, aluminoborosilicates, fluoroaluminosilicates, barium silicates, barium aluminosilicates, barium aluminoborosilicates, strontium aluminosilicates, barium fluoroaluminosilicates, strontium fluoroaluminosilicates, strontium zinc fluoroaluminosilicates, zinc aluminosilicates, prepolymerization fillers, and combinations thereof. In some embodiments, the filler is present in an amount of about 10% (w / w) to about 90% (w / w). In more specific embodiments, the filler is present in an amount of about 40% (w / w) to about 80% (w / w). In even more specific embodiments, the filler is present in an amount of about 60% (w / w) to about 80% (w / w).

[0019] In some embodiments, the composition comprises a photoinitiator, a stabilizer, a solvent, or any combination thereof. In some embodiments, the photoinitiator is present in an amount of about 5% (w / w) or less. In further or alternative embodiments, the stabilizer is present in an amount of about 1% (w / w) or less.

[0020] In some embodiments, the compositions provided herein are free from or substantially free from acids or anhydrides. In certain embodiments, the composition (and / or part thereof) contains less than 5% (w / w) of acid (e.g., less than 3% (w / w), less than 1% (w / w), or less than 0.5% (w / w)). In certain embodiments, the composition or part thereof is non-acidic (e.g., has a pH of about 5 or higher).

[0021] In various embodiments, the compositions provided herein have good performance characteristics, such as when used in restorative dental applications (e.g., in the restoration of teeth with Class I or Class II cavities). In certain embodiments, by combining the first and second parts, the total volume of the composition shrinks by less than 10% (e.g., less than 8%, less than 6%, or less than 4%) (e.g., as it hardens). In some cases, minimizing such shrinkage reduces the incidence of void formation between the filling and the tooth, and reduces the incidence of tooth damage (e.g., cracking) during and after restoration. In further or alternative embodiments, by combining the first and second parts, the hygroscopicity of the composite material is 100 μg / mm³. 3 Less than (for example, 50 μg / mm³) 3 Less than 25 μg / mm³ 3 Less than 20 μg / mm³ 3 Less than 15 μg / mm³ 3 (less than). In some cases, minimizing hygroscopicity reduces the expansion of the restorative material, which then hardens into a composite material, potentially reducing the occurrence of tooth damage (e.g., cracking) and detachment of the filling from the tooth.

[0022] Also provided herein are dental composites resulting from mixtures of the compositional components or portions described herein, for example, partially or fully cured mixtures. In some embodiments, the composite comprises a partially or fully cured resin, a filler, and copper. In certain embodiments, the composite comprises about 10% (w / w) to about 60% (w / w) of the cured resin, about 10% (w / w) to about 90% (w / w) of the filler, and less than about 1 elemental weight percent of copper. Also provided herein are reaction mixtures comprising a copper(II) catalyst; a hydroperoxide; a polymerizable monomer containing an ethylenic group; and thiourea. The reaction mixture is partially cured, with some of its monomer units forming monomers and others forming oligomers or polymers thereof.

[0023] In some embodiments, the two-part composition provided herein is contained within a dual-barrel apparatus comprising a housing comprising a first barrel and a second barrel, the first barrel containing the first part of the composition described herein and the second barrel containing the second part of the composition described herein. In certain embodiments, the dual-barrel apparatus is configured to extrude and / or mix the first and second parts simultaneously.

[0024] Methods for restoring a solid tooth are also provided herein. In some embodiments, the method involves combining a first composition (e.g., a first part of the dental composition described herein) with a second composition (e.g., a second part of the dental composition described herein) to form a mixed composition. In certain embodiments, the first composition comprises a hydroperoxide, and the second composition comprises thiourea, as well as one or both of the first and / or second compositions comprising a copper(II) catalyst, a polymerizable monomer (e.g., a polymerizable monomer containing an ethylene group), and a filler. In some embodiments, the method further comprises administering the mixed composition to a solid (e.g., a class I or class II cavity in a solid tooth). In some embodiments, the method further comprises curing the mixed composition (e.g., self-curing the composition, and / or photocuring the composition using dental curing light). In certain embodiments, curing of the mixed composition results in the formation of a restorative composite (e.g., in the form of a filling in the solid tooth cavity). In preferred embodiments, the curing step (e.g., self-curing) is performed relatively quickly to facilitate the restorative process. In certain embodiments, the curing process (e.g., self-curing or solidification) occurs within 10 minutes, 4 minutes, 2 minutes, etc.

[0025] In a particular embodiment, the method of the present invention includes: 1) applying a dental adhesive primer to dentin and enamel (e.g., tooth structure), optionally followed by the application of a hardening agent, and optionally curing the primer layer with dental hardening light; 2) applying a dental adhesive primer to a pre-fabricated restoration such as a crown, inlay, onlay, or veneer, optionally followed by the application of a hardening agent, and optionally curing the primer layer with dental hardening light; and 3) applying a dental cement layer to bond the pre-fabricated restoration to the tooth structure (dentin and enamel).

[0026] In some embodiments, the method includes removing the cavity from the inside and around the cavity to be filled (for example, by perforating the tooth and removing the cavity from there).

[0027] These and other purposes, properties, characteristics of compositions, parts thereof, precursors thereof, resulting composites, and methods disclosed herein, along with methods of manufacture, will be made clearer by considering the following description and appended claims and referring to the appended drawings (all of which form part of this specification). However, it should be clearly understood that the drawings are for illustrative and explanatory purposes only and are not intended as limiting definitions of the invention. As used in the specification and claims, the singular forms “a,” “an,” and “the” refer to multiple subjects unless the context clearly indicates otherwise. Specific Description of the Invention

[0028] This specification provides dental compositions. It also provides their components, dental restorative methods, resins used in the preparation of dental compositions, and dental composites (e.g., fillings). In certain embodiments, a dental composition comprises two parts, such as two parts that are kept physically separated from each other. In some cases, the two parts are combined to form a composite (e.g., a filling used in tooth restoration), for example, when the dental composition is used in a dental restorative method (as described herein).

[0029] In certain embodiments, provided herein are dental compositions comprising two parts (e.g., with free radical polymerization initiated by mixing them), wherein in some embodiments the two-part dental composition comprises: (1) at least one monomer having at least one ethylenically unsaturated group (e.g., also referred to as a polymerizable monomer containing an ethylenically active group, as described herein); (2) a part comprising at least one hydroperoxide group; and (3) a part comprising at least one substituted thiourea. In more specific embodiments, the two-part dental composition comprises: (1) at least one monomer having at least one ethylenically unsaturated group; (2) a part comprising at least one hydroperoxide group; (3) a part comprising at least one substituted thiourea; and (4) at least one copper(II) compound (e.g., a copper(II) compound that, when combined with the first and second parts, catalytically affects the curing of the composition, for example, simplifying and / or accelerating (e.g., polymerization of its monomer components)).

[0030] In certain embodiments, provided herein are dental compositions comprising a first part and a second part, wherein the first part comprises a polymerizable monomer comprising: (1) a copper(II) catalyst; (2) a hydroperoxide; and (3) an ethylenic group, and the second part comprises: (1) a copper(II) catalyst; (2) thiourea; and (3) an ethylenic group. Also provided herein are individual first and second parts, such as dental compositions comprising a polymerizable monomer comprising: (1) a copper(II) catalyst; (2) a hydroperoxide; and (3) an ethylenic group, and / or dental compositions comprising a polymerizable monomer comprising: (1) a copper(II) catalyst; (2) thiourea; and (3) an ethylenic group.

[0031] In certain embodiments, a dual-barrel device is provided that includes a housing, the housing including a first barrel and a second barrel, the first barrel containing therein a first portion of the composition described herein, and the second barrel containing a second portion of the composition provided herein. In some embodiments, the dual-barrel device is any suitable device adapted to simultaneously extrude the first and second portions, such that the first and second portions are mixed and the initialization and polymerization of their monomer components is promoted. In certain embodiments, the dual-barrel device is a dual-barrel syringe that includes a nozzle configured to promote mixing of the first and second portions by (simultaneous) depression including first and second plungers.

[0032] In certain embodiments, a monomer having at least one ethylenically unsaturated group or a polymerizable monomer containing an ethylenic group is a compound containing at least one >C=C< group. In certain embodiments, the monomer is represented by the formula R2C=CR2, where each R is independently selected from H, COOR 1 , or an optionally substituted hydrocarbon such as alkyl, aryl, where at least one R is not H. In certain embodiments, at least one R is COOR 1 or aryl (e.g., phenyl, etc.). In some embodiments, R 1is either H or alkyl (e.g., C1-C6 alkyl). In a more specific embodiment, the alkyl is C1-C6 alkyl (e.g., methyl, ethyl, etc.). In a particular embodiment, the alkyl is acyclic (e.g., branched or linear) or cyclic, saturated or unsaturated alkyl. In some embodiments, optional substituents include, non-limiting examples, -OH, alkyl, and / or aryl. In a particular embodiment, the monomer comprises one or more moieties represented by the formula R2C=CRL, where the R and L groups are independently as described above for the R group. In a particular embodiment, the monomer comprises two or more R2C=CRL groups, where the L groups are linked together as shown in formula I (e.g., R2C=CRL-(LCR=CR2)). a They are linked together as shown, and in the expression a>0, for example 1 to 5, for example 1 to 2). [ka]

[0033] For example, in some embodiments, the monomer may be R2C=CR-COO((CH2) m (CHOH) n ) p OOC - RC = CR2, where m is between 1 and 6 (e.g., 2 and 4), n is between 0 and 1, and p is between 1 and 30 (e.g., 1 and 10).

[0034] In a particular embodiment, the monomer is an acrylate (for example, three R groups are H and one R group is COOR). 1 ), methacrylate (for example, two R groups are H, one R group is methyl, and another R group (on the same carbon as the methyl group) is COOR) 1The monomer is either a acrylate, a methacrylate, and / or a vinyl group (at least one R group is a hydrocarbon). In some embodiments, the monomer comprises an acrylate, a methacrylate, and / or a vinyl group. In certain embodiments, the ethylenically unsaturated group is selected from acrylate and methacrylate groups. Examples of polymerizable monomers include, but are not limited to, glycerol di(meth)acrylate, glycerol mono(meth)acrylate, hydroxyethyl(meth)acrylate {(meth)acrylate = acrylate or methacrylate}, hydroxypropyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2'-ethoxy-2-ethoxyethyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate; polyethylene glycol mono(meth)acrylate, polyethylene glycol di-(meth)acrylate, polypropylene glycol mono-(meth)acrylate Examples include (meth)acrylates, polypropylene glycol di-(meth)acrylates, polytetramethylene glycol mono-(meth)acrylates, polytetramethylene glycol di-(meth)acrylates, hexanediol di(meth)acrylates, octanediol di(meth)acrylates, decanediol di(meth)acrylates, trimethyloylpropane tri(meth)acrylates, urethane dimethacrylates (reaction adducts of 2-hydroxyethyl methacrylate with 2,4,4-trimethylhexanediisocyanate), 2,2-bis[4-(2-hydroxy-3-methacryloylpropoxy)-phenyl]-propane (Bis-GMA), ethoxylated bisphenol A dimethacrylate in tetrahydrofurfuryl (meth)acrylate (where the total number of moles of ethylene oxide in the molecule can range from 2 to 30 units), or mixtures thereof. As referred to herein, “(meth)acrylate” includes disclosures of both methacrylates and acrylates.

[0035] In a particular embodiment, the amount of monomer present in the composition is any preferred amount. In a particular embodiment, the dental composition provided herein contains 10% to 60% monomer by weight percentage (for example, of the entire composition). In a more specific embodiment, the weight percentage is between 20% and 50%.

[0036] In certain embodiments, the compositions provided herein contain copper(II), such as in the form of copper(II) compounds. In certain examples, copper(II) (e.g., copper(II) compounds) is used to catalyze the curing (e.g., hardening or setting) of the composition (e.g., to accelerate or facilitate the polymerization of monomers). In certain examples, the presence of copper(II) (e.g., its compounds) facilitates the polymerization process when two parts of the composition of the present invention are mixed (e.g., the hydroperoxide and thiourea separated thereby come together, facilitating the initiation of polymerization, which is facilitated by the presence of copper(II)). The copper(II) catalyst may be in a dissociated form, an associated form (e.g., in the form of copper(II) compounds), or a partially associated form. In various embodiments, the copper(II) compound is any suitable compound whose molecular formula contains at least one copper(II). Examples of copper(II) compounds include, but are not limited to, copper(II) sulfate, copper(II) acetate, copper(II) chloride, copper(II) acetylacetone, and combinations thereof. In certain embodiments, the copper(II) compound is copper(II) acetate. In other embodiments, the copper(II) compound is copper(II) acetylacetone. In certain embodiments, the weight percentage of copper(II) (or its compounds) is less than 1%. In more specific embodiments, the weight percentage of copper(II) (or its compounds) is less than 0.1%. In even more specific embodiments, copper(II) (or its compounds) is provided in the compositions herein in an amount of about 0.001% to about 0.05% by weight, or is combined with other materials.

[0037] In certain embodiments, the hydroperoxide is such that, when combined with any suitable agent, particularly dentally acceptable agents, such as thiourea provided herein, the polymerization of the monomer herein is initiated and / or accelerated at a rate suitable for dental applications, particularly restorative applications. In some embodiments, the hydroperoxide is of the formula HOO-R 2 It is expressed as, and in the formula R 2 R is any suitable organic group. In a particular embodiment, R 2 C4~C 20 These are hydrocarbons (optionally substituted with any preferred group such as alkyl groups, aryl groups (e.g., phenyl), alkylaryl groups, or additional -OOH groups). In some embodiments, R 2 The formula is: -CR 3 R 4 R 5 It is expressed by, in the formula, R 3 , R 4 , and R 5 Each of these is independently H, alkyl (cyclic and / or acyclic, and branched or linear), aryl (e.g., phenyl), arylalkyl (e.g., bonded to the carbon of an alkyl), alkylarylalkyl, etc., where such groups are optionally substituted or unsubstituted. In some embodiments, R 3 , R 4 , and R 5 At least two of them are not H. In a particular embodiment, the hydroperoxide is a tertiary hydroperoxide, i.e., R 3 , R 4 , and R 5 None of these are H. In certain cases, R 3 , R 4 , and / or R 5 One or more of the following are different or the same R 3 , R 4 , and R 5They are optionally combined to form a cyclic (monocyclic or polycyclic) alkyl group (which may be substituted or unsubstituted as described herein). Any preferred hydroperoxide compound having at least one hydroperoxide group may be used as described herein. In certain embodiments, the hydroperoxide compound contains more than one hydroperoxide group. Non-limiting examples of hydroperoxide compounds include, without limitation, t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinan hydroperoxide, p-methane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0038] In some embodiments, any preferred concentration of hydroperoxide is optionally utilized in the compositions and methods provided herein. In certain embodiments, the total amount of hydroperoxide compounds is in the range of about 0.01% (w / w) to about 10.0% (w / w) (e.g., of the whole composition). In certain embodiments, the hydroperoxide is present in the range of about 0.1% (w / w) to about 5.0% (w / w) of the whole composition. In some embodiments, the hydroperoxide is present in the composition in an amount of about 1.5% (w / w) to about 5% (w / w). In certain examples, the hydroperoxides provided herein, such as those described above, are stable under various conditions and have long storage life.

[0039] Any suitable thiourea may be used as desired in the compositions described herein (for example, in at least a portion of the two-part compositions described herein). In some embodiments, the thiourea is a substituted thiourea, such as dentally acceptable thiourea. In some embodiments, the thiourea is an organic thiourea, for example, a thiourea substituted with an organic radical (e.g., pyridyl, acetyl). In certain embodiments, the thiourea is structure R 6 R 7 NC(=S)NR 8 R9 It is expressed by, in the formula, R 6 , R 7 , R 8 and R 9 H, COR 10 , independently selected from heterocycloalkyl and heteroaryl (e.g., substituted or unsubstituted heterocycloalkyl or heteroaryl), R 10 is alkyl, heteroalkyl (cyclic or acyclic), aryl, or heteroaryl (R 10 (is substituted or unsubstituted). In certain embodiments, the thiourea group is bonded to the heteroatom of the ring at the α-carbon position to a heterocycloalkyl or heteroaryl group. In some embodiments, R 6 , R 7 , R 8 and R 9 At least one or more of the atoms are not H. In certain embodiments, the substituted thioureas are selected from the group consisting of 1-(2-pyridyl)-2-thiourea (PTU), 1-benzoyl-2-thiourea (BTU), 1-acetyl-2-thiourea (ATU), 1-(2-tetrahydrofurfuryl)-2-thiourea (TTU) and mixtures thereof (i.e., one or more of PTU, BTU, ATU, and / or TTU).

[0040] In certain embodiments, a combination of two parts of the composition provided herein results in the curing of the composition. In certain examples, a combination of two parts, particularly a hydroperoxide and its thiourea, facilitates the initiation of polymerization of the monomer components of the composition. In certain embodiments, the inclusion of a copper(II) catalyst accelerates the curing process (e.g., polymerization of monomer components) and results in a curing time fast enough to be suitable for dental applications. In some cases, when the two parts are mixed, the mixed composition cures (sets or hardens, etc.). In one embodiment, the setting time is less than 20 minutes (e.g., without the need for photocuring using a photocuring device that emits most light having wavelengths in the blue range (e.g., 400 nm to 530 nm, about 470 nm, etc.)). In one embodiment, the setting time is less than 10 minutes. In one embodiment, the setting time is less than 5 minutes. In a more preferred embodiment, the curing (e.g., setting) time is about 250 seconds or less. In a preferred embodiment, the curing (e.g., setting) time is about 180 seconds or less. In further or alternative embodiments, the composition, when the two parts are combined, has a working time of about 200 seconds or less, for example, about 150 seconds or less. Furthermore, in some embodiments, the working time is at least 30 seconds (for example, to enable the restoration or filling of a tooth cavity, particularly a Class I or Class II cavity).

[0041] In certain embodiments, the composition and / or a portion thereof may include additional additives. In some embodiments, and as non-limiting examples, any suitable additives may be included, such as photoinitiators, fillers, stabilizers, solvents, or combinations thereof. In certain embodiments, the dental composition (or a portion thereof) includes a resin composition and a filler (e.g., a resin composition containing the materials of the dental composition described herein). In more specific embodiments, each portion of the composition provided herein includes a resin composition (e.g., a composition containing the monomers described herein) and a filler.

[0042] In certain embodiments, the compositions (or parts thereof) provided herein include fillers, for example, at least one type of pulverized filler. In some cases, the fillers may reduce polarization shrinkage, improve mechanical properties, and enhance the radiopaqueness of the dental composite. In further or alternative examples, the fillers may alter the rheological properties of the dental composition. Exemplary fillers include, but are not limited to, metal oxides, metal nitrides, metal fluorides, silicate glass, colloidal silica, precipitated silica, fused silica, aluminosilicate glass, aluminoborosilicate glass, fluoroaluminosilicate glass, barium silicate, barium aluminoborosilicate, barium aluminoborosilicate, strontium aluminosilicate, barium fluoroaluminosilicate, strontium zinc fluoroaluminosilicate, zinc aluminosilicate prepolymerized composite fillers, and any one or more combinations thereof. Examples of metal oxides and fluorides include, but are not limited to, barium oxide, strontium fluoride, barium fluoride, ytterbium fluoride, yttrium fluoride, zinc oxide, and bismuth(III) oxide. In one embodiment, the filler is treated with a coupling agent such as γ-methacryloyloxypropyltrimethoxysilane (MPTMS). In some examples, such treatment strengthens the interfacial bond between the filler and the resin matrix and improves the mechanical properties.

[0043] In some embodiments, the filler is a pulverized filler, for example, a filler comprising or composed of multiple solid particles. In certain embodiments, the pulverized filler (e.g., its particles) has any preferred average size (e.g., particle size) between 0.02 microns (μm) and 30 microns. In certain embodiments, the average size is between 0.2 microns and 10 microns.

[0044] In certain embodiments, the filler is present in any preferred amount in the composition provided herein. In some embodiments, the filler (e.g., a pulverized filler) is present in the composition in an amount between 10% and 90% by weight. In certain embodiments, the weight percentage is between 40% and 80%.

[0045] In certain embodiments, the compositions (or parts thereof) provided herein further comprise at least one photoinitiator. Any suitable photoinitiator may optionally be included. Examples of photoinitiators include, but are not limited to, benzoin and its derivatives, 2,2-diethoxyacetophenone, camphoroquinone, 1-phenyl-1,2-propanedione, monoacylphosphine oxides, bisacylphosphine oxides, and mixtures thereof. Furthermore, activators may be used together with the photoinitiators. Examples of activators include, but are not limited to, 2-ethyl-4-(N,N-dimethylamino)benzoate, 2-amyl-4-(N,N-dimethylamino)benzoate, 2-octyl-4-(N,N-dimethylamino)benzoate; 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminophenethyl alcohol, and mixtures thereof. In one embodiment, the photoinitiator system includes camphoroquinone and 2-ethyl-4-(N,N-dimethylamino)benzoate, 2-amyl-4-(N,N-dimethylamino)benzoate, 2-octyl-4-(N,N-dimethylamino)benzoate; 2-(ethylhexyl)-4-(N,N-dimethylamino)benzoate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminophenethyl alcohol, and any one or more mixtures thereof. In one embodiment, the weight percentage of the photoinitiator is less than 5%. In one embodiment, the weight percentage of the photoinitiator is less than 3%.

[0046] In certain embodiments, the compositions provided herein include at least one stabilizer. In some cases, the stabilizer is an agent that inhibits polymerization, such as the monomer components of the compositions described herein. In certain examples, such agents are useful for improving the shelf life of the compositions provided herein (e.g., inhibiting the polymerization of monomers before use). Any suitable stabilizer or polymerization inhibitor (such as a free radical scavenger) may be optionally used herein. Non-limiting examples of stabilizers include 2,6-di-(tert-butyl)-4-methylphenol (BHT) and 4-methoxyphenol (MEHQ). The stabilizer may be used in any suitable amount, for example, less than 1% by weight.

[0047] In certain embodiments, provided herein are methods of using and preparing such compositions in or for dental applications. In general examples, such compositions are prepared in a dentally acceptable manner (i.e., in a manner suitable for administration to an individual, a patient, or a person's mouth (or dental cavity)). In certain embodiments, provided herein are methods of administering the compositions described herein to an individual, for example, to restore the teeth of the individual. In certain embodiments, the compositions described herein are provided, any part thereof, to be combined to form a mixed composition (e.g., the monomers of the compositions are polymerized), the mixed composition is administered to an individual (e.g., a cavity in the individual), and the mixed composition is cured (e.g., until it hardens).

[0048] In certain embodiments, this method is used to restore teeth (e.g., teeth containing cavities). In some embodiments, the composition is administered, delivered, and / or used to restore teeth containing Class I or Class II cavities (e.g., based on the GV Black classification system), or cavities in posterior teeth. In certain embodiments, Class I cavities are cavities located in recesses or fissures on the occlusal surfaces of molars and premolars, two-thirds of the occlusal surface of the buccal surface of molars, the lingual surface of upper incisors, or the lingual surface of upper molars. In some embodiments, Class II cavities are cavities on the proximal surface of molars or premolars. In certain embodiments, the composition is particularly useful in providing an effective mechanism for filling large cavities (areas where other restorative compositions are lacking). In certain embodiments, a cavity treated according to the method herein has a depth of about 3 mm or more (e.g., about 4 mm or more, about 5 mm or more, about 5 mm to about 7 mm, etc.) from the surface of any tooth (e.g., the surface of a tooth filling, or the location of the tooth surface that was there before the cavity, or the location that would have been there if there had been no cavity).

[0049] In some embodiments, the mixture is further cured by dental curing light, for example, after it has solidified under intraoral conditions. In further or alternative embodiments, an additional layer of the dental composition provided herein is placed on top of a solidified or cured mixture and subsequently cured by dental curing light.

[0050] In certain embodiments, portions of the compositions provided herein are mixed to form a mixed composition, which is administered to a solid (e.g., a dental cavity of a solid), and the mixed composition is cured under ambient conditions for up to 15 minutes (e.g., 0.2 to 15 minutes, 0.5 to 10 minutes, 1 to 6 minutes, 2 to 5 minutes, or 3 to 4 minutes, etc.). In certain examples, curing under ambient conditions involves curing the composition (e.g., curing in the absence of a photoinitiator such as a light-emitting device, the majority of which has blue wavelengths (e.g., in the range of 400 to 530 nm, or about 470 nm)). In certain embodiments, the cured (e.g., self-cured or solidified) composite is further cured using a photoinitiator such as a light-emitting device, the majority of which has blue wavelengths (e.g., 400 to 530 nm, or about 470 nm). In more specific embodiments, an additional mixed composition is administered to the cavity before photocuring. In some cases, photocuring on the surface is desirable to facilitate the complete curing of the filler on the surface (for example, the radical groups of the living polymer and / or initiator may interact and die in air before complete polymerization / curing).

[0051] In some embodiments, one or more properties of the desired restorative materials described herein are achieved in any preferred manner, such as by using the concentrations of the materials described herein. In certain embodiments, those provided herein are compositions containing copper(II) as described herein (e.g., bipartite compositions). In some embodiments, the presence of copper(II) catalyzes the hardening (e.g., self-hardening) of the composition at a rate sufficient to be dentally effective. In some embodiments, the amount of copper(II) (or its compounds) present is not very necessary to exert the effect. For example, in some embodiments, less than 0.1% by weight or less than 0.01% by weight per layer of copper(II) (or its compounds) is used. In further or alternative embodiments, a good hardening rate is achieved by using higher concentrations of hydroperoxide and / or thiourea. In some embodiments, the compositions provided herein include a total concentration of hydroperoxide and thiourea of ​​about 2.5% by weight or more (for example, hydroperoxide and thiourea are provided in separate parts of the composition) (relative to the total weight of monomers, i.e., {{weight hydroperoxide + weight thiourea} / total weight monomer} × 100%), about 3% by weight or more, about 4% by weight or more, or about 5% by weight or more.

[0052] In certain embodiments of this specification, dental cements are provided comprising a cured combination of a first and a second part of any composition herein, or a cured combination of any composition comprising a hydroperoxide as described herein and any composition comprising thiourea. In certain embodiments, one or both parts of the compositions described herein comprise a copper(II) catalyst. In some embodiments, composites provided herein comprise a curing resin (e.g., a polymerization monomer as described herein), a filler, and copper. In certain embodiments, the composite comprises a curing resin in any preferred amount (e.g., about 10% to about 60% by weight), such as in the amount described herein for a composition comprising a monomer, a filler in any preferred amount (e.g., about 10% to about 90% by weight), and copper in an amount of about 1% by weight or less (e.g., based on the amount of copper present on an elemental basis) (e.g., about 0.1% by weight or less, about 0.05% by weight or less, etc.). In a particular embodiment, the dental composite material contains approximately 60% (w / w) to 80% (w / w) of filler and approximately 20% (w / w) to 40% (w / w) of curing resin.

[0053] In certain embodiments, the dental cement compositions provided and used herein have no or low acid and / or anhydride content. In certain embodiments, the acid and / or anhydride content is less than 5% by weight of the composition. In more specific embodiments, the acid and / or anhydride content is less than 3% by weight of the composition, less than 2% by weight of the composition, less than 1% by weight of the composition, less than 0.5% by weight of the composition, less than 0.1% by weight of the composition, and so on. In some embodiments, the compositions are substantially neutral or alkaline, such as having a pH of about 5 or higher, about 5.5 or higher, about 6 or higher, about 6.5 or higher, or about 7 or higher. In certain cases, the acid content of the composition is preferably kept to a minimum for any reason, such as minimizing the hygroscopicity or moisture absorption of the resulting composite. In some cases, if moisture absorption into the composite is at a high level when used as a restorative material, the volume of the restorative material may expand, the restorative material may deform, and ultimately lead to detachment of the restorative material, tooth damage, and / or other undesirable consequences.

[0054] In certain embodiments, the compositions provided herein contain approximately 100 μg / mm³ of 3 The composite material (or the composite material provided herein) hardens to the following moisture sorption. In a particular embodiment, the moisture sorption is approximately 50 μg / mm³. 3 Below, approximately 25μg / mm 3 Below, about 20μg / mm 3 The following, or approximately 15 μg / mm³ 3 That is the case.

[0055] In some embodiments, the composite materials described herein (e.g., formed from a combination of the compositional parts described herein) have good physical parameters for dental applications. In some embodiments, such composite materials have good flexural strength (e.g., above 50 MPa, above 100 MPa, above 125 MPa, etc.). In further or alternative embodiments, the composite materials have good compressive strength (e.g., above 100 MPa, above 150 MPa, above 200 MPa, above 250 MPa, etc.). In certain embodiments, the composite materials have good diametrical strength (e.g., above 30 MPa, above 40 MPa, above 45 MPa, etc.). In some embodiments, the composite materials provided herein have good water solubility (e.g., 1 μg / mm³). 3 (In some embodiments, composites provided herein have good water solubility (e.g., less than 1 μg / mm3)). In certain embodiments, the composites provided herein have good radiopaqueness (e.g., greater than 200% Al, greater than 300% AI, etc.). Any such parameters may be determined using any preferred process, such as testing a film containing such a composite (e.g., a film having a thickness of about 10 to 15 microns, e.g., about 14 microns).

[0056] This specification also provides methods for producing the compositions described herein. In some embodiments, the components of the compositions described herein are combined in any preferred order. Exemplary processes are described in the examples. In certain embodiments, some of the compositions provided herein are prepared by combining monomers, hydroperoxides, optional stabilizers, and optional photoinitiators. In some embodiments, these combinations are mixed to form a resin, to which fillers are added, and then mixed or milled. Similarly, some of the compositions provided herein are prepared in certain embodiments by combining monomers, thiourea, optional stabilizers, and optional photoinitiators. In some embodiments, these combinations are mixed to form a resin, to which fillers are added, and then mixed or milled. Examples of specific agents (and corresponding component types) described in the examples should be understood as being included in the disclosure of compositions and methods described herein.

[0057] Ceramics are inorganic nonmetallic solid materials containing metallic, nonmetallic, or metalloid atoms, primarily held together by ionic and covalent bonds. In dentistry, ceramic materials are widely used to manufacture dental crowns, and typical ceramic materials include, but are not limited to, zirconium oxide, feldspar porcelain, and lithium disilicate. A primer may be required before cementation to ensure good adhesive strength to these materials.

[0058] It is also possible to fabricate tooth crowns using pre-cured dental resin, and a primer may be necessary to obtain sufficient adhesive strength.

[0059] In some embodiments, the method includes: 1) applying a dental bonding primer to the dentin and enamel, then optionally applying a hardening activator, and optionally hardening the primer layer with a dental hardening light; 2) applying a dental bonding primer to a pre-fabricated restoration such as a crown, inlay, onlay, or veneer, adding a hardening activator as needed, and hardening the primer layer with a dental hardening light as needed; and 3) applying a dental cement layer to bond the pre-fabricated restoration to the tooth structure (dentin and enamel).

[0060] In some embodiments, the dental adhesive primer comprises at least one polymerizable monomer having at least one phosphate pendant group. In some embodiments, the monomer is selected from the group consisting of ethylene glycol methacrylate phosphate, bis[2-(methacryloyloxy)ethyl] phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, glycerol phosphate di(meth)acrylate, phenyl-P (phenyl methacrylate phosphate), and PENTA-P (dipentaerythritol pentaacrylate phosphate).

[0061] In some embodiments, the dental adhesive primer comprises at least one polymerizable monomer having at least one carboxylic acid or anhydride pendant group. In some embodiments, the monomer is selected from the group consisting of (meth)acrylic acid, maleic anhydride, trimellitic anhydride, 4-META (4-methacrylateoxyethyl trimellitic anhydride), maleic anhydride, trimellitic anhydride, 4-META (4-methacrylateoxyethyl trimellitic anhydride); PM-HEMA (addition product of pyromellitic anhydride and 2-hydroxyethyl methacrylate), PM-GDM (addition product of pyromellitic anhydride and glycerol dimethacrylate), BTDA-HEMA (addition product of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and hydroxyethyl methacrylate), PA-HEMA (addition product of phthalic anhydride and hydroxyethyl methacrylate), and MA-GDM (addition product of maleic anhydride and glycerol dimethacrylate).

[0062] In some embodiments, the dental adhesive primer comprises at least one ethylenically unsaturated group having at least one (meth)acrylate group. In certain embodiments, the ethylenically unsaturated group is selected from acrylate groups and methacrylate groups. Examples of polymerizable monomers include, but are not limited to, glycerol di(meth)acrylate, glycerol mono(meth)acrylate, hydroxyethyl(meth)acrylate {(meth)acrylate = acrylate or methacrylate}, hydroxypropyl(meth)acrylate, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, octyl(meth)acrylate, decyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2'-ethoxy-2-ethoxyethyl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate; polyethylene glycol mono-(meth)acrylate, polyethylene glycol di-(meth)acrylate, polypropylene glycol Mono(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, polytetramethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, octanediol di(meth)acrylate, decanediol di(meth)acrylate, trimethyloylpropane tri(meth)acrylate, urethane dimethacrylate (a reaction adduct of 2-hydroxyethyl methacrylate with 2,4,4-trimethylhexanediisocyanate), 2,2-bis[4-(2-hydroxy-3-methacryloylpropoxy)-phenyl]-propane (Bis-GMA), ethoxylated bisphenol A dimethacrylate in tetrahydrofurfuryl(meth)acrylate (the total number of moles of ethylene oxide in the molecule may range from 2 to 30 units), or mixtures thereof. As referred to herein, “(meth)acrylate” includes disclosures of both methacrylate and acrylate.

[0063] In some embodiments, the dental adhesive primer comprises at least one solvent. In some embodiments, the solvent is selected from the group consisting of ethanol, isopropanol, n-propanol, n-butanol, t-butanol, acetone, methyl ethyl ketone, and water.

[0064] In some embodiments, the curing agent is a chemical substance that generates free radicals in an acidic environment.

[0065] In some embodiments, the material of the prefabricated restoration is a pre-cured dental resin containing at least one inorganic filler. In some embodiments, the material of the prefabricated restoration is ceramic. In some embodiments, the ceramic is selected from the group consisting of zirconium oxide, feldspar porcelain, and lithium disilicate.

[0066] In some embodiments, the dental primer on a pre-fabricated restoration is a dental adhesive. In some embodiments, the dental primer is a primer comprising at least one silane having at least one (meth)acrylate pendant group.

[0067] In some embodiments, dental cement is delivered to the pre-fabricated restoration via a dental dual-barrel syringe equipped with a mixing tip.

[0068] In some embodiments, excess dental cement is removed with a dental instrument. In some embodiments, the dental cement is optionally cured with dental curing light.

[0069] In some examples, as used herein, “set time” is the length of time it takes for a mixed composition provided herein (i.e., a composition combining both parts of a two-part composition described herein) to form a solid or hard composite (partially or completely cured) in the absence of auxiliary devices designed to facilitate the curing of restorative materials, such as dental curing lights (also referred to herein as “self-curing”). Dental curing lights are dental devices used for the polymerization of composite materials based on photocurable resins. They can be used with several different dental materials that cure with light. The light used falls within the visible blue light spectrum. This light is supplied across various wavelengths and differs depending on the type of device. There are four basic types of dental curing lights: tungsten halogen, light-emitting diode (LED), plasma arc curing (PAC), and laser. In certain examples, “work time” is the length of time after the mixed composition has become non-adaptive using typical dental techniques and / or equipment.

[0070] As used herein, weight percentage (wt%) or %(w / w) means the percentage of the weight of an ingredient relative to the total weight of a composition or composite, unless otherwise specified. In some embodiments, weight percentage refers to the weight of an ingredient relative to the weight of a two-part composition (e.g., one in which the first and second parts are physically separated), and / or the weight of an ingredient relative to the weight of a part of a two-part composition. In some cases, the weight percentages of an ingredient may be the same or similar in both parts of a two-part system, or the ingredient may have different weight percentages in each part of a two-part system. For example, in a common example, hydroperoxide and thiourea each have different weight percentages in their respective parts, with the hydroperoxide being present entirely or primarily in the first part of the composition, and the thiourea being present entirely or primarily in the second part of the composition.

[0071] As used herein, the term "alkyl" refers, alone or in combination, to a linear or branched saturated or unsaturated hydrocarbon monoradical which has, for example, 1 to about 10, more preferably 1 to about 6 carbon atoms. Examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, tert-amyl and hexyl, as well as longer-chain alkyl groups such as heptyl and octyl. Where used herein, numerical ranges such as "C1-C6 alkyl" mean, in some embodiments, that the alkyl group consists of one carbon atom, in some embodiments, two carbon atoms, in some embodiments, three carbon atoms, in some embodiments, four carbon atoms, in some embodiments, five carbon atoms, or in some embodiments, six carbon atoms. However, this definition also covers instances of the term "alkyl" where no numerical range is specified. Furthermore, in cases where the alkyl group is substituted on both sides (e.g., as described for L above), alkyl may refer to the monoradical or diradical derived from the alkyl group as defined above. Examples include, but are not limited to, methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), and isopropylene (-CH(CH3)CH2-)."Alkyl" can also refer to cyclic alkyl groups, which are optionally substituted saturated hydrocarbon monoradical rings containing, for example, 3 to about 15 ring carbon atoms or 3 to about 10 ring carbon atoms, but in some embodiments include additional acyclic carbon atoms as substituents (e.g., methylcyclopropyl). This term includes fusion, non-fusion, crosslinking, and spiroradicals. In some embodiments, condensed cycloalkyls include 2 to 4 condensed rings, the bonding ring being a cycloalkyl ring. Examples include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, cumene, and pinaring systems.

[0072] As used herein, the term “aryl” refers to an aromatic hydrocarbon radical having 6 to about 20 ring carbon atoms, either alone or in combination, with optional substitutions, and includes condensed and uncondensed aryl rings. A condensed aryl ring radical contains 2 to 4 condensed rings, the ring of this bond being an aryl ring, and the other individual rings being alicyclic, heterocyclic, aromatic, heteroaromatic, or any combination thereof. Furthermore, the term “aryl” also includes condensed and uncondensed rings containing 6 to about 12 ring carbon atoms, as well as those containing 6 to about 10 ring carbon atoms. Non-limiting examples of monocyclic aryl groups include phenyl; examples of condensed ring aryl groups include naphthyl, phenantrenyl, anthracenyl, and azlenyl; and an example of an uncondensed bi-aryl group is biphenyl.

[0073] As used herein, the term “heteroaryl” refers to an optionally substituted aromatic monoradical containing, alone or in combination, about 5 to about 20 skeletal ring atoms, wherein one or more ring atoms are heteroatoms independently selected from oxygen, nitrogen, and sulfur (but not limited to these atoms), provided that the ring of the group does not contain two adjacent O or S atoms. In embodiments where two or more heteroatoms are present in the ring, the two or more heteroatoms are either identical to each other or some or all of the two or more heteroatoms are different from the others. The term heteroaryl includes optionally substituted fused and unfused heteroaryl groups having at least one heteroatom. The term heteroaryl also includes condensed and uncondensed heteroaryls having 5 to about 12 skeletal ring atoms, as well as those having 5 to about 10 skeletal ring atoms. In certain examples, the bond to the heteroaryl group is via carbon atoms or heteroatoms. Non-limiting examples of monocyclic heteroaryl groups include pyridyl or furanyl.

[0074] As used herein, the term “heteroalkyl” refers to the optionally substituted alkyl structures described above, in which one or more carbon atoms (and any associated hydrogen atoms as may be) of the skeletal chain are independently substituted with heteroatoms (i.e., atoms other than carbon, such as oxygen, nitrogen, sulfur, or any combination thereof, without limitation). Exemplary heteroalkyl groups include linear groups such as ethylene oxide (e.g., -CH2CH2On-) or cyclic groups such as tetrahydrofuran. [Examples]

[0075] The abbreviations for the materials used in the example are as follows: PTU: 1-(2-pyridyl)-2-thiourea CHP: Cumene hydroperoxide CuPD: Acetylacetone copper(II) MDP: 10-Methacryloyloxydecyl dihydrogen phosphate R202: AEROSIL (trademark) fumed silica R812S: AEROSIL (trademark) fumed silica GM27884-K6: Schott GM27884 dental glass, 3μm YbF3: Ytterbium fluoride BYK W9010: Wet Dispersion Additive (Flow Modifier) CQ: Camphorquinone EDMAB: Ethyl-4-dimethylaminobenzoate UDMA: Urethane dimethacrylate E6BAD: Ethoxylated (6) bisphenol A dimethacrylate EBPADM: Ethoxylated (3) bisphenol A dimethacrylate BisGMA: Bisphenol A-glycidyl methacrylate TEGDM: Triethylene glycol dimethacrylate BHT: Butylated hydroxytoluene HDK N-20P: Fumed Silica Pluronic L-44: Surfactant DI water: Distilled water DHEPT:NN-bis(2-hydroxyethyl)-p-toluidine BPO: Benzoyl peroxide

[0076] Example 1 - Preparation of adhesive containing 16% MDP Examples 1 and 2 were prepared by adding and mixing chemicals. The chemicals were mixed until all solids except fumed silica were dissolved, resulting in a low-viscosity liquid.

[0077] [Table 1]

[0078] Example 2 - Preparation of an adhesive containing 8% MDP and 8% PMDM Example 2 was prepared by mixing Examples 1 and 2 in the specified ratio.

[0079] [Table 2]

[0080] Comparative Example A - Preparation of an adhesive containing 0% MDP and 16% PMDM Examples 1 and 2 were prepared by adding and mixing chemicals. All chemicals were mixed until all solids except fumed silica were dissolved, producing a low-viscosity liquid.

[0081] [Table 3]

[0082] Example 3 - Preparation of Part 1 CHP-Co-Initiator Containing Paste Example 3 was prepared by adding and mixing chemicals. The resin chemical was mixed with soluble solids such as CQ, EDMAB, and BHT until all the solids were dissolved. Then, solid fillers containing R812S, YbF3, and GM27884 were added and mixed in a speed mixer, followed by mixing in a three-roll mill to obtain a paste-like semi-solid.

[0083] [Table 4]

[0084] Example 4 - Preparation of a second portion PTU-co-initiator-containing paste Example 4 was prepared by adding and mixing chemicals. The resin chemical was mixed with soluble solids containing CQ, EDMAB, PTU, and BHT until all solids were dissolved. CuPD was added to the TEGDMA mixer and mixed in a speed mixer. Next, solid fillers containing R812S, YbF3, and GM27884 were added and mixed in a speed mixer, and then mixed in a three-roll mill to obtain a paste-like semi-solid.

[0085] [Table 5]

[0086] Example 5 - Preparation of a mixture of the paste from Example 3 (Part 1) and the paste from Example 4 (Part 2) Example 5 was prepared by filling dual-barrel syringes with Example 3 (containing CHP co-initiator) and Example 4 (containing PTU co-initiator), with one paste in each barrel as the first and second portions. When using this paste combination, a mixing tip is attached to allow both pastes to pass through the mixing barrel and be properly mixed. Once mixed, the material cured in approximately 4–8 minutes.

[0087] Examples 7 and 8 and Comparative Example B - Application of adhesive and mixed first and second parts of cement paste. A zirconia substrate was embedded in a polymer resin and exposed by cutting off the top layer. The exposed substrate was polished with 600-grit SiC paper. The zirconia surface was further sandblasted with 50 nm aluminum oxide powder at a pressure of 60 psi. All test specimens were then thoroughly rinsed. A layer of adhesive from either Example 1, Example 2, or Comparative Example A was applied by light brushing and then thinned with air for approximately 10 seconds. The test specimens were then placed in an adhesive jig as described in ISO 29022-2013. The paste mixture from Example 5 was injected into the cavity and held in a humid chamber at 35°C for 1 hour before being removed from the jig. The test specimens were then placed in water and held in an oven at 37°C for 20 hours. The adhesive strength of the test specimens was then recorded according to ISO 29022-2013. For 10 test specimens in each group, the average adhesive strength and standard deviation were recorded in Table 1. The results showed that MDPs containing 16% (Example 1) or 8% (Example 2) of adhesive provided adhesive strengths exceeding 15 MPa at 19.8 MPa and 19.1 MPa, respectively, while the adhesive of Comparative Example A, which lacked MDP, had inferior adhesive strength of less than 15 MPa at 11.6 MPa.

[0088] [Table 6]

[0089] Comparative Example C - Preparation of Part 1 BPO-Co-Initiator Containing Paste Comparative Example C was prepared by adding and mixing chemicals as in Example 3. The resin chemical was mixed with soluble solids such as CQ, EDMAB, BPO, and BHT until all solids were dissolved. Then, solid fillers containing R812S, YbF3, and GM27884 were added and mixed in a speed mixer, followed by a three-roll mill to obtain a paste-like semi-solid.

[0090] [Table 7]

[0091] Comparative Example D - Second Part: Preparation of DHEPT-Co-Initiator-Containing Paste Comparative Example D was prepared by adding and mixing chemicals as in Example 4. The resin chemical was mixed with soluble solids such as CQ, EDMAB, DHEPT, and BHT until all solids were dissolved. Then, solid fillers containing R812S, YbF3, and GM27884 were added and mixed in a speed mixer, followed by a three-roll mill to obtain a paste-like semi-solid.

[0092] [Table 8]

[0093] Comparative Example E - Preparation of a mixture of the paste from Part 1 of Example C and the paste from Part 2 of Example D Comparative Example E was prepared as in Example 5 by filling a dual-barrel syringe with Comparative Examples C and D, each containing one paste. When using this paste combination, a mixing tip is attached to ensure that both pastes pass through the mixing cylinder and mix properly. Once mixed, the materials cured in approximately 4–8 minutes.

[0094] Comparative Examples F and G - Application of Adhesive and Mixed First and Second Parts of Cement Paste As in Examples 7 and 8, the zirconia substrate was embedded in polymer resin and exposed by cutting off the top layer. The exposed substrate was polished with 600-grit SiC paper. The zirconia surface was further sandblasted with 50 nm aluminum oxide powder at a pressure of 60 psi. All specimens were then thoroughly rinsed. The layer from Example 1 or Example 2 was applied by light brushing and then thinned with air for about 10 seconds. The specimens were then placed in the bonding jig described in ISO 29022-2013. The paste mixture from Comparative Example E was injected into the cavity and held in a humid chamber at 35°C for 1 hour before being removed from the jig. The specimens were then placed in water and held in an oven at 37°C for 20 hours. The bonding strength of the specimens was then recorded according to ISO 29022-2013. For 10 specimens in each group, the average bonding strength and standard deviation were recorded in Table 2. The results shown in Table 2 indicate that when BPO (Example C) and DHEPT (Example D) are used as co-initiators in the first and second co-initiator-containing pastes for preparing cement paste, the adhesive strength is significantly lower and weaker at 8.1 MPa and 11.4 MPa compared to when CHP (Example 3) and PTU (Example 4) are used as co-initiators in the first and second parts at 19.8 MPa and 19.1 MPa, respectively.

[0095] [Table 9]

Claims

1. A dental composition comprising a paste mixture, The paste mixture is formed by mixing together a first portion and a second portion that have been separated beforehand, wherein the first portion comprises at least one polymerizable monomer and at least one hydroperoxide, wherein the hydroperoxide is cumene hydroperoxide (CHP), and the second portion comprises at least one thiourea compound, wherein the thiourea is 1-(2-pyridyl)-2-thiourea (PTU), The first or second portion of the paste mixture further comprises a copper(II) compound. The dental composition wherein the at least one polymerizable monomer comprises at least one of ethoxylated (6) bisphenol A dimethacrylate and ethoxylated (3) bisphenol A dimethacrylate.

2. The dental composition according to claim 1, wherein the dental composition further comprises an adhesive, the adhesive strength of the adhesive on a dental substrate is 15 MPa, the dental substrate is zirconia, and the adhesive comprises 8% to 16% 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP).

3. The dental composition according to claim 2, wherein the adhesive is an adhesive in a single bottle.

4. A method for preparing a dental paste mixture, A method comprising the step of mixing a first part and a second part, which are separated from each other, using an apparatus, to form the dental paste mixture, wherein the paste mixture from the apparatus comprises in the first part at least one polymerizable monomer and at least one hydroperoxide, wherein the hydroperoxide is cumene hydroperoxide (CHP) and the second part at least one thiourea compound, wherein the thiourea is 1-(2-pyridyl)-2-thiourea (PTU), and the first part or the second part of the paste mixture further comprises a copper(II) compound, and the at least one polymerizable monomer comprises at least one of ethoxylated (6) bisphenol A dimethacrylate and ethoxylated (3) bisphenol A dimethacrylate.

5. The method according to claim 4, wherein the apparatus is a dual-barrel syringe.

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